Azo dyes having a benzoisothiazolyl diazo component

ABSTRACT

P-aminoazo dyes of the formula: ##STR1## in which D is a benzoisothiazolyl group; 
     B 1  is hydrogen, methyl, ethyl, methoxy, ethoxy; 
     B 2  is hydrogen, methyl, ethyl, methoxy, ethoxy, chloro, bromo, C 1  to C 4  alkanoylamino or C 1  to C 4  alkoxycarbonylamino; 
     R 1  is the radical ##STR2##  C 1  to C 4  alkyl optionally bearing hydroxy, C 1  to C 4  alkoxy, C 1  to C 4  alkanoyloxy, C 1  to C 4  alkoxycarbonyl, C 1  to C 4  alkanoylamino or chloro as a substituent, phenylethyl, phenoxyethyl or cyclohexyl and the group -A 1  --CO--A 2  represents acyl, acyloxy or acylamino derived from a carbonic acid derivative in which A 1  is a single bond, --O--, --NH-- or ##STR3##

The invention relates to dyes of the formula (I): ##STR4## in which D is a radical of the formula: ##STR5## X is nitro, chloro or bromo; Y is hydrogen, chloro or bromo;

Z is hydrogen, chloro, bromo or cyano;

B¹ is hydrogen, methyl, ethyl, methoxy, ethoxy or phenoxy;

B² is hydrogen, methyl, ethyl, methoxy, ethoxy, chloro, bromo, C₁ to C₄ alkanoylamino or C₁ to C₄ alkoxycarbonylamino;

R¹ is C₁ to C₄ alkyl optionally bearing hydroxy, C₁ to C₄ alkoxy, C₁ to C₄ alkanoyloxy, C₁ to C₄ alkoxycarbonyl, C₁ to C₄ alkanoylamino or chloro as a substituent, cyclohexyl, phenylethyl, phenoxyethyl or a radical of the formula: ##STR6## A¹ is a direct bond, --O--, --NH-- or ##STR7## A² is a radical of the formula ##STR8##

or (when A¹ is --NH-- or --O--) may also be --O--A⁵ ;

A³ is hydrogen, C₁ to C₈ alkyl optionally bearing hydroxy, C₁ to C₄ alkoxy, chloro, cyano, C₁ to C₄ alkoxycarbonyl, C₁ to C₄ alkanoylamino, C₁ to C₄ alkylaminocarbonyloxy, C₁ to C₄ alkoxycarbonyloxy or C₁ to C₄ alkanoyloxy as a substituent, allyl, cyclohexyl, benzyl, or phenyl optionally bearing chloro, bromo, methyl or C₁ to C₄ alkoxycarbonyl as a substituent;

A⁴ is hydrogen or C₁ to C₄ alkyl optionally bearing hydroxy, chloro, C₁ to C₄ alkoxy or C₁ to C₄ alkanoyloxy as a substituent;

A⁵ is C₁ to C₄ alkyl optionally bearing hydroxy, chloro, C₁ to C₄ alkoxy, C₁ to C₄ alkanoyloxy or C₁ to C₄ alkylaminocarbonyloxy as a substituent, cyclohexyl or phenyl; and

Q is a radical of the formula ##STR9##

Examples of alkanoylamino radicals B² are: butyrylamino, propionylamino, formylamino and particularly acetylamino and also NHCOOCH₃, NHCOOC₂ H₅, NHCOOC₃ H₇ and NHCOOC₄ H₉.

Examples of radicals R¹ other than those already specified are: C₂ H₄ OC₃ H₇, C₂ H₄ OC₄ H₉, C₂ H₄ OCOC₄ H₉, C₂ H₄ OCOC₃ H₇, C₂ H₄ OCOC₂ H₅, ##STR10## C₂ H₄ COOC₄ H₉, C₃ H₆ NHCOCH₃, C₂ H₄ COOC₃ H₇, C₂ H₄ Cl, particularly CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₂ H₄ OH, C₂ H₄ CN, CH₂ CHOHCH₃, C₂ H₄ OCH₃, C₂ H₄ OC₂ H₅, C₂ H₄ OCOCH₃, C₂ H₄ COOCH₃ and C₂ H₄ COOC₂ H₅.

Examples of radicals Q--A¹ --CO--A² are: C₂ H₄ CONHCH₃, C₂ H₄ CON(CH₃)₂, C₂ H₄ CONHC₂ H₅, C₂ H₄ CON(C₂ H₅)₂, ##STR11## C₂ H₄ CONHC₃ H₇, C₂ H₄ CONHC₄ H₉, C₂ H₄ CON(C₄ H₉)₂, ##STR12## C₂ H₄ CONHC₂ H₄ CN, ##STR13## C₂ H₄ CONHC₂ H₄ OCH₃, C₂ H₄ CONHC₃ H₆ OCH₃, C₂ H₄ CONHC₂ H₄ OC₂ H₅, C₂ H₄ CONHC₂ H₄ OC₂ H₄ OH, C₂ H₄ CONHC₂ H₄ OH, ##STR14## C₂ H₄ CON(C₂ H₄ OH)₂, C₂ H₄ CONHC₃ H₆ OH, C₂ H₄ CONHCH₂ CHOHCH₃, C₂ H₄ CONHC₂ H₄ OCOCH₃, C₂ H₄ CONHC₂ H₄ OCOC₃ H₇, ##STR15## C₂ H₄ CONHC₃ H₆ OCOCH₃, C₂ H₄ CONHC₂ H₄ OCONHCH₃, C₂ H₄ CONHC₂ H₄ OCONHC₄ H₉, C₂ H₄ CONHC₂ H₄ OCOOCH₃, C₂ H₄ CONHC₂ H₄ NHCOCH₃, C₂ H₄ CONHC₂ H₄ NHCOC₃ H₇, C₂ H₄ OCONH₂, C₂ H₄ OCONHCH₃, ##STR16## C₂ H₄ OCON(CH₃)₂, C₂ H₄ OCONHC₂ H₅, C₂ H₄ OCON(C₂ H₅)₂, C₂ H₄ OCONHCH₂ -CH═CH₂, C₂ H₄ OCONHC₃ H₇, C₂ H₄ OCONHC₄ H₉, C₂ H₄ OCON(C₄ H₉)₂, C₂ H₄ OCONHC₅ H₁₁, C₂ H₄ OCONH(CH₂)₅ CN, C₂ H₄ OCONHC₆ H₁₃, C₂ H₄ OCONHC₇ H₁₅, C₂ H₄ OCONHC₈ H₁₇, ##STR17## C₂ H₄ OCONHCH₂ COOCH₃, C₂ H₄ OCONHCH₂ COOC₂ H₅, C₂ H₄ OCONH(CH₂)₂ COOCH₃, C₂ H₄ OCONH(CH₂)₃ COOCH₃, C₂ H₄ OCONHC₂ H₄ Cl, C₂ H₄ OCONHC₂ H₄ OCOCH₃, C₂ H₄ OCONHC₂ H₄ OH, C₂ H₄ OCONHC₃ H₆ OH, C₂ H₄ OCONHC₂ H₄ CN, C₂ H₄ OCON(C₂ H₄ CN)₂, ##STR18## C₂ H₄ OCOOC₂ H₄ OCH₃, C₂ H₄ OCOOC₃ H₆ OCH₃, C₂ H₄ OCOOC₂ H₄ OC₂ H₅, CH₂ CH₂ OCH₂ CH₂ OCOOCH₃, C₂ H₄ OCOOC₂ H₄ Cl, ##STR19## C₃ H₆ NHCON(CH₃)₂, C₃ H₆ NHCONHC₂ H₅, C₃ H₆ NHCON(C₂ H₅)₂, C₃ H₆ NHCONHC₃ H₇, C₃ H₆ NHCONHC₄ H₉, C₂ H₄ NHCONHC₄ H₉, C₃ H₆ NHCONHC₆ H₁₃, ##STR20## C₃ H₆ NHCONHCH₂ COOCH₃, C₃ H₆ NHCONHCH₂ COOCH₂ H₅, C₃ H₆ NHCONH(CH₂)₂ COOCH₃, C₃ H₆ NHCONHC₂ H₄ CN, ##STR21## C₃ H₆ NHCOOC₂ H₄ OCH₃, C₃ H₆ NHCOOC₂ H₄ OC₂ H₅, C₃ H₆ NHCOOC₃ H₆ OCH₃, C₃ H₆ NHCOOC₂ H₄ Cl, C₂ H₄ NHCOOC₂ H₄ OH, C₃ H₆ NHCOOC₂ H₄ OH, C₃ H₆ NHCOOC₃ H₆ OH, C₃ H₆ NHCOOC₂ H₄ OCOCH₃, C₃ H₆ NHCOOC₂ H₄ OCONHCH₃, ##STR22##

Dyes of the formula (Ia): ##STR23## in which D¹ is 5-nitrobenzoisothiazolyl-(2,1), 5-nitro-7-bromobenzoisothiazolyl-(2,1), 7-nitrobenzoisothiazolyl-(1,2), 5-bromo-7-nitrobenzoisothiazolyl-(1,2) or 5-cyano-7-nitrobenzoisothiazolyl-(1,2);

B³ is hydrogen, methoxy or ethoxy;

B⁴ is hydrogen, chloro, methyl, acetylamino or propionylamino; and

R² is C₁ to C₄ alkyl, C₁ to C₄ alkoxyethyl, C₁ to C₄ alkoxypropyl, β-cyanoethyl, β-chloroethyl, β-hydroxyethyl, β-hydroxypropyl, β-C₁ to C₄ alkanoyloxyethyl, β-C₁ to C₄ alkanoyloxypropyl, C₁ to C₄ alkoxycarbonyl, phenylethyl or a radical of the formula ##STR24## in which A¹ and A² have the above meanings are of particular technical importance.

Examples of preferred radicals ##STR25## are: C₂ H₄ CONHCH₃, C₂ H₄ CONHC₂ H₅, C₂ H₄ CONHC₃ H₇, C₂ H₄ CONHC₄ H₉, C₂ H₄ CONHC₂ H₄ OCH₃, C₂ H₄ CONHC₃ H₆ OCH₃, C₂ H₄ CONHC₂ H₄ OH, ##STR26## C₂ H₄ CONHC₃ H₆ OH, C₂ H₄ CONHCH₂ CHOHCH₃, C₂ H₄ CONHC₂ H₄ OCOCH₃, C₂ H₄ NHC₂ H₄ OCOC₃ H₇, ##STR27## C₂ H₄ CONHC₃ H₆ OCOCH₃, C₂ H₄ CONHC₂ H₄ OCONHCH₃, C₂ H₄ CONHC₂ H₄ OCONHC₄ H₉, C₂ H₄ OCONHCH₃, ##STR28## C₂ H₄ OCON(CH₃)₂, C₂ H₄ OCON(C₂ H₅)₂, C₂ H₄ OCONHC₃ H₇, C₂ H₄ OCONHC₄ H₉, C₂ H₄ OCONHCH₂ COOC₂ H₅, C₂ H₄ OCONHCH₂ COOCH₃, C₂ H₄ OCONHC₂ H₄ Cl, ##STR29## C₂ H₄ OCOOC₂ H₅, C₂ H₄ OCOOC₃ H₇, C₂ H₄ OCOOC₄ H₉, ##STR30## C₂ _(H) ₄ OCOOC₂ H₄ OCH₃, C₂ H₄ OCOOC₃ H₆ OCH₃, C₂ H₄ OCOOC₂ H₄ Cl; C₃ H₆ NHCONHCH₃, C₃ H₆ NHCON(CH₃)₂, C₃ H₆ NHCON(C₂ H₅)₂, C₃ H₆ NHCONHC₃ H₇, C₃ H₆ NHCONHC₄ H₉, C₃ H₆ NHCONHCH₂ COOC₂ H₅, ##STR31## C₃ H₆ NHCOOCH₃, C₃ H₆ NHCOOC₂ H₅, C₃ H₆ NHCOOC₃ H₇, C₃ H₆ NHCOOC₄ H₉, ##STR32## C₂ H₄ OCOOC₂ H₄ OCH₃, C₂ H₄ OCOOC₃ H₆ OCH₃, C₂ H₄ OCOOC₂ H₄ OC₂ H₅, C₃ H₆ NHCOOC₂ H₄ Cl and C₃ H₆ NHCOOC₂ H₄ OH.

Particularly preferred meanings are:

D¹ : 5-nitrobenzoisothiazolyl-(2,1), 7-nitrobenzoisothiazolyl-(1,2), 5-bromo-7-nitrobenzoisothiazolyl-(1,2) or 5-cyano-7-nitrobenzoisothiazolyl-(1,2);

B³ : hydrogen;

B⁴ : hydrogen, methyl or acetylamino; and

R² : methyl, ethyl, methoxyethyl, β-cyanoethyl, β-hydroxyethyl, or a radical of the formula ##STR33##

Particularly preferred radicals ##STR34## are:

C₂ H₄ CONHC₂ H₄ OH, ##STR35## C₂ H₄ CONHC₃ H₆ OH, C₂ H₄ CONHCH₂ CHOHCH₃, C₂ H₄ CONHC₂ H₄ OCOCH₃, ##STR36## C₂ H₄ CONHC₃ H₆ OCOCH₃, C₂ H₄ OCONHCH₃, C₂ H₄ OCON(CH₃)₂, C₂ H₄ OCONHC₄ H₉, C₃ H₆ NHCONHCH₃, C₃ H₆ NHCONHC₄ H₉, C₃ H₆ NHCOOCH₃ and C₃ H₆ NHCOOC₂ H₄ OH.

Dyes of the formula (I) may be prepared by reacting a diazonium compound of an amine of the formula (II):

    d--nh.sub.2                                                (ii)

with a coupling component of the formula (III): ##STR37## where D, B¹, B², R¹, A¹ and A² have the above meanings, the diazotization and coupling being carried out as usual.

Dyes of the formula (I) are red to greenish blue and are suitable for dyeing synthetic and cellulosic fibers and particularly cellulose esters and polyesters.

Dyeings are obtained which show deep shades and generally have very good wet and light fastness properties and also resistance to high temperatures. In the case of dyes suitable for cellulose esters the very good fastness to gas fume fading, dry cleaning and perspiration may be stressed and in the case of the polyester dyes fastness to thermofixation and fastness properties after thermofixation.

The following Examples illustrate the invention. In them the references to parts and percentages are by weight unless otherwise stated.

EXAMPLE 1

19.5 parts of 3-amino-5-nitro-2,1-benzoisothiazole is introduced into 100 parts of 85% sulfuric acid at from 10° to 15° C. 30 parts of nitrosylsulfuric acid (with a content of 13.1% of dinitrogen trioxide) is dripped into this solution at 0° to 5° C. The diazo solution obtained is stirred for another three hours at 0° to 5° C. and then dripped into a solution of 25 parts of N-ethyl-N-β-[N'-methyl-N'-(β-hydroxyethyl)]-carbamoyl-ethylaniline, 40 parts of 10% hydrochloric acid, 500 parts of water, 500 parts of ice and 1 part of sulfamic acid. The whole is then neutralized to pH 1.5 with sodium acetate solution, and the precipitated dye is suction filtered, washed with water until neutral and dried at subatmospheric pressure at 50° C. 31 parts of the dye of the formula: ##STR38## is obtained; it gives on polyesters and preferentially on cellulose esters intense blue dyeings with good fastness properties and particularly good fastness to light, wet treatment and dry cleaning.

EXAMPLE 2

9.7 Parts of 4-amino-7-nitro-1,2-benzoisothiazole is introduced at 10° to 15° C. into 100 parts of 85% sulfuric acid. 15 parts of nitrosylsulfuric acid (with a content of 13.1% of dinitrogen trioxide) is dripped into this solution at from 0° to 5° C. The diazo solution obtained is stirred for another three hours at 0° to 5° C. and then dripped into a solution of 13.9 parts of N-ethyl-N-β-(N'-β-acetoxyethyl)-carbamoylethyl-aniline, 20 parts of 10% hydrochloric acid, 250 parts of water, 250 parts of ice and 1 part of sulfamic acid. Neutralization to pH 1.5 is then carried out with sodium acetate solution, the precipitated dye is suction filtered, washed with water until neutral and dried at subatmospheric pressure at 50° C. 31 parts of the dye of the formula: ##STR39## is obtained which gives intense violet dyeings having good fastness properties on polyesters and cellulose esters.

EXAMPLE 3

19.5 Parts of 3-amino-5-nitro-2,1-benzoisothiazole is introduced at from 10° to 15° C. into 100 parts of 85% sulfuric acid. 30 parts of nitrosylsulfuric acid (having a content of 13.1% of dinitrogen trioxide) is dripped into this solution at 0° to 5° C. The diazo solution obtained is stirred for another three hours at from 0° to 5° C. and then dripped into a solution of 22.2 parts of N-ethyl-N-[β-(methylaminocarbonyloxy)-ethyl]-aniline, 40 parts of 10% hydrochloric acid, 500 parts of water, 500 parts of ice and 1 part of sulfamic acid. The whole is then neutralized to pH 1 with sodium acetate solution. The precipitated dye is suction filtered, washed with water until it is neutral and dried at subatmospheric pressure at 50° C. 32 parts of the dye of the formula: ##STR40## is obtained. It gives intense blue dyeings with good fastness properties on polyesters and cellulose esters.

EXAMPLE 4

19.5 Parts of 3-amino-5-nitro-2,1-benzoisothiazole is introduced at from 10° to 15° C. into 100 parts of 85% sulfuric acid. 30 parts of nitrosylsulfuric acid (13.1% of N₂ O₃) is dripped into this solution at from 0° to 5° C. The diazo solution obtained is stirred for 3 hours at from 0° to 5° C. and then dripped into a solution of 26.4 parts of N-ethyl-N-[β-(n-butylaminocarbonyloxy)-ethyl]-aniline, 40 parts of 10% hydrochloric acid, 500 parts of water, 500 parts of ice and 1 part of sulfamic acid. The whole is then neutralized to pH 1.5 with sodium acetate. The precipitated dye is suction filtered, washed with water until it is neutral and dried at 50° C. at subatmospheric pressure. 33 parts of the dye of the formula ##STR41## is obtained which gives intense blue dyeings with good fastness properties on polyesters.

EXAMPLE 5

13.7 Parts of 4-amino-5-bromo-7-nitro-1,2-benzoisothiazole is dissolved in 100 parts of 96% sulfuric acid at from 10° to 15° C. Then 30 parts of a mixture (17:3) of glacial acetic acid and propionic acid is gradually added to the solution at from 0° to 5° C. and diazotization is effected by dripping in 15 parts of nitrosylsulfuric acid (13.1% of N₂ O₃) at 0° to 5° C. The whole is stirred for another three hours at 0° to 5° C. and the diazo solution is run into a solution of 13.2 parts of N-ethyl-N-[β-(n-butylcarbamoyloxy)ethyl]-aniline, 20 parts of 10% hydrochloric acid, 250 parts of water, 200 parts of ice and 1 part of sulfamic acid. The pH is adjusted to 1.5 with sodium acetate solution, and the precipitated dye is suction filtered, washed with water until it is neutral and dried at subatmospheric pressure at 50° C. 22 parts of the dye of the formula: ##STR42## is obtained. It gives an intense reddish blue having good fastness properties on polyesters.

EXAMPLE 6

5.5 Parts of 4-amino-5-cyano-7-nitrobenzoisothiazole-(1,2) is introduced at 10° C. into a mixture of acids consisting of 50 parts of 85% sulfuric acid and 15 parts of a mixture (17:3) of glacial acetic acid and propionic acid. 9.5 parts of nitrosylsulfuric acid (11.1% N₂ O₃) is added at from 0° to 5° C. and the mixture is stirred for four hours at this temperature. Excess nitrosylsulfuric acid is destroyed in the usual way. The diazo solution is added in portions to a solution, cooled to from 0° to 5° C., of 9.6 parts of N-ethyl-N-[-β-(n-butylamino-carbonyloxy)-ethoxy]-m-toluidine in 100 parts by volume of glacial acetic acid and at the same time 250 parts of ice is introduced gradually. After the coupling is completed the dye is suction filtered, washed with water until it is neutral and dried at 50° C. at subatmospheric pressure.

10.4 parts of the dye of the formula: ##STR43## is obtained. It gives very intense dyeings having outstanding fastness properties on polyesters.

EXAMPLE 7

19.5 Parts of 3-amino-5-nitro-2,1-benzoisothiazole is introduced at from 10° to 15° C. into 100 parts of 85% sulfuric acid. 30 parts of nitrosylsulfuric acid (having a content of 13.1% of dinitrogen trioxide) is dripped in at from 0° to 5° C. The diazo solution obtained is stirred at from 0° to 5° C. for three hours and then dripped into a solution of 26.6 parts of N-ethyl-N-(carbo-β-oxyethoxyaminopropyl)-aniline, 40 parts of 10% hydrochloric acid, 500 parts of water, 500 parts of ice and 1 part of sulfamic acid. Then the pH is adjusted to 1 with sodium acetate solution. The precipitated dye is suction filtered, washed with water until it is neutral and dried at 50° C. at subatmospheric pressure. 33 parts of the dye of the formula: ##STR44## is obtained. It gives intense blue dyeings having good fastness properties on polyesters and cellulose esters.

EXAMPLE 8

9.7 Parts of 4-amino-7-nitrobenzoisothiazole-(1,2) is introduced into 100 parts of 85% sulfuric acid at from 10° to 15° C. 15 parts of nitrosylsulfuric acid (with a content of 13.1% of dinitrogen trioxide) is dripped into this solution at from 0° to 5° C. The diazo solution obtained is stirred for another 3 hours at 0° to 5° C. and then dripped into a solution of 14.0 parts of N-ethyl-N-(carbo-β-oxyethoxy-aminopropyl)-m-toluidine, 40 parts of 10% hydrochloric acid, 500 parts of water, 500 parts of ice and 1 part of sulfamic acid. The pH is then adjusted to 1 with sodium acetate solution. The precipitated dye is suction filtered, washed with water until it is neutral and dried at 50° C. at subatmospheric pressure. 34 parts of the dye of the formula: ##STR45## is obtained. It gives intense violet dyeings on polyesters and cellulose esters.

EXAMPLE 9

5.5 Parts of 4-amino-5-cyano-7-nitrobenzoisothiazole-(1,2) is introduced at 10° C. into a mixture of acids consisting of 50 parts of 85% sulfuric acid and 15 parts by volume of a mixture (17:3) of glacial acetic acid and propionic acid. 9.5 parts of nitrosylsulfuric acid (11.1% of N₂ O₃) is added at from 0° to 5° C. and the mixture is stirred for four hours at this temperature. The excess of nitrosylsulfuric acid is destroyed as usual. The diazo solution is added in portions to a solution, cooled to 0° to 5° C., of 5.5 parts of N-ethyl-N-[γ-(methoxycarbonylamino)-propyl-]aniline in 100 parts by volume of glacial acetic acid and 250 parts of ice is gradually added at the same time. When the coupling has been completed the dye is suction filtered, washed with water until it is neutral and dried at 50° C. at subatmospheric pressure. 8.7 parts of the dye of the formula: ##STR46## is obtained. It dyes polyesters full blue hues having good fastness properties.

EXAMPLE 10

5.5 parts of 4-amino-5-cyano-7-nitrobenzoisothiazole is introduced at 10° C. into a mixture of acids consisting of 50 parts 85% sulfuric acid and 15 parts by volume of a mixture (17:3) of glacial acetic acid and propionic acid. 9.5 parts of nitrosylsulfuric acid (M = 342) is added thereto at from 0° to 5° C. and the mixture is stirred for 4 hours at this temperature. The excess of nitrosylsulfuric acid is destroyed in the usual way. The diazo solution is added in portions to a solution, cooled to 0° to 5° C., of 6.9 parts of N-ethyl-N-[γ-(n-butylaminocarbonylamino)-propyl]-aniline in 100 parts by volume of glacial acetic acid and at the same time 250 parts of ice is gradually introduced. After the coupling is ended the dye is suction filtered, washed with water to make it neutral and dried at 50 ° C. at subatmospheric pressure. 9.8 parts of the dye of the formula: ##STR47## is obtained. It gives intense blue dyeings having good fastness properties on polyesters.

Dyes of the formula (I) which are hereinafter characterized by specifying their substituents are also obtained by methods analogous to those described in Examples 1 to 10.

      No. DK B.sup.1 B.sup.2 R.sup.1 alkylene A.sup.1 A.sup.2 Hue                 11       ##STR48##       H H C.sub.2 H.sub.4 OH C.sub.2 H.sub.4 -- NHCH.sub.3 blue 12 " H H      C.sub.2 H.sub.5 C.sub.2 H.sub.4 -- NHC.sub.2 H.sub.4 OH " 13 " H H      CH.sub.2 CHOHCH.sub.2 Cl C.sub.2 H.sub.4 -- NHC.sub.2 H.sub.4 OH " 14 "      H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 -- NHC.sub.3 H.sub.6 OH " 15 " H H      C.sub.2 H.sub.5 C.sub.2 44 -- NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH " 16      " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 -- NHCH.sub.2 CHOHCH.sub.3 " 17 "      H H C.sub.2 H.sub.5 C.sub.2       H.sub.4 --      ##STR49##       " 18 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 -- NHC.sub.2 H.sub.4      OCOCH.sub.3 " 19 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 -- NHC.sub.2      H.sub.4 NHCOCH.sub.3 " 20 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.4 O      NHCH.sub.3 " 21 " H CH.sub.3 CH.sub.3 C.sub.2 H.sub.4 O NHCH.sub.3 " 22      " H H C.sub.2 H.sub.4 OCH.sub.3C.sub.2 H.sub.4 O NHCH.sub.3 " 23 " H      NHCOCH.sub.3 C.sub.2 H.sub.4 OCONHCH.sub.3 C.sub.2 H.sub.4 O NHCH.sub.3      greenish blue 24 " H H C.sub.2 H.sub.4 COOCH.sub.3 C.sub.2 H.sub.4 O      NHCH.sub.3 blue 25 " H CH.sub.3 C.sub.2 H.sub.4 OCONHCH.sub.3 C.sub.2      H.sub.4 O NHCH.sub.3 " 26 " H H C.sub.2       H.sub.5      ##STR50##       O NHCH.sub.3 " 27 " H H C.sub.2       H.sub.5      ##STR51##       O NHCH.sub.3 " 28 " H H C.sub.2 H.sub.5 C.sub.2       H.sub.4 O N(CH.sub.3).sub.2 " 29 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4      O NHCH.sub.2 COOC.sub.2 H.sub.5 " 30 " H H C.sub.2 H.sub.4 OCOCH.sub.3      C.sub.2 H.sub.4 O NHC.sub.2 H.sub.4 Cl " 31 " H H C.sub.2 H.sub.5      C.sub.2 H.sub.4 O NHC.sub.2 H.sub.4 OH " 32 " H H C.sub.2 H.sub.5      C.sub.2       H.sub.4 O      ##STR52##       " 33 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.4 O NHC.sub.4 H.sub.9 "      34 " H CH.sub.3 CH.sub.3 C.sub.2 H.sub.4 O NHC.sub.4 H.sub.9 " 35 "      OCH.sub.3 NHCOCH.sub.3 C.sub.2 H.sub.4 CN C.sub.2 H.sub.4 O NHC.sub.4      H.sub.9 greenish blue 36 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.4 O      NH(CH.sub.2).sub.5 CN blue 37 " H H C.sub.2 H.sub.4 CN C.sub.2 H.sub.4 O      OCH.sub.3 bluish violet 38 " H H C.sub.2 H.sub.4 OCOOCH.sub.3 C.sub.2      H.sub.4 O OCH.sub.3 " 39 " H H C.sub.2 H.sub.4 OC.sub.2 H.sub.5 C.sub.2      H.sub.4 O OC.sub.2 H.sub.4 Cl " 40 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4      O OC.sub.4 H.sub.9 " 41 " H H C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH      NHCH.sub.3 blue 42 " H H C.sub.2 H.sub.5 C.sub.3 H.sub.6 NC.sub.2      H.sub.4 CN NHC.sub.4 H.sub.9 " 43 " H H C.sub.2 H.sub.5 C.sub.3 H.sub.6      NH N(CH.sub.3).sub.2 " 44 " H H C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH       ##STR53##       " 45 " H H C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH OCH.sub.3 " 46 " H H      CH.sub.3 C.sub.3 H.sub.6 NH OCH.sub.3 " 47 " H CH.sub.3 C.sub.2 H.sub.5      C.sub.3 H.sub.6 NH OC.sub.2 H.sub.4 OH " 48 " H H C.sub.2 H.sub.5      C.sub.2 H.sub.4 NH OC.sub.2 H.sub.4 OH " 49 " H H C.sub.2 H.sub.5      C.sub.3 H.sub.6 NH OC.sub.2 H.sub.4 OCOCH.sub.3 " 50 " H H C.sub.2      H.sub.5 C.sub.3       H.sub.6 NH      ##STR54##       " 51       ##STR55##       H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 -- NHC.sub.2 H.sub.4 OCOCH.sub.3      greenish blue 52 " H H C.sub.4 H.sub.9 C.sub.2 H.sub.4 -- NHC.sub.2      H.sub.4 OCONHCH.sub.3 " 53 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 --      NHC.sub.2 H.sub.4 OCH.sub.3 " 54 " H H C.sub.2       H.sub.5      ##STR56##       O NHCH.sub.3 " 55 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 O NHC.sub.4      H.sub.9 " 56 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 O NH(C.sub.4       H.sub.9).sub.2 " 57 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 O NHCH.sub.2      COOC.sub.2 H.sub.5 " 58 " H H C.sub.2 H.sub.5 C.sub.2       H.sub.4 O NHCH.sub.2CHCH.sub.2 " 59 " H H C.sub.2 H.sub.5 C.sub.2      H.sub.4 O       ##STR57##       " 60 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 O OCH.sub.3 " 61 " H H       ##STR58##       C.sub.2 H.sub.4 O OCH.sub.3 " 62 " H H C.sub.2 H.sub.5 C.sub.3 H.sub.6      NH NHC.sub.4 H.sub.9 " 63 " H H C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH       ##STR59##       " 64 " H H C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH NHCH.sub.3 " 65 " H H      C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH OC.sub.2 H.sub.4 OH " 66 " H CH.sub.3      CH.sub.3 C.sub.3 H.sub.6 NH OC.sub.2 H.sub.4 OH " 67 " H H C.sub.2      H.sub.5 C.sub.3 H.sub.6 NH OC.sub.2 H.sub.4 OCONHC.sub.4 H.sub.9 " 68 "      H CH.sub.3 C.sub.2 H.sub.5 C.sub.3       H.sub.6 NH      ##STR60##       " 69       ##STR61##       H H C.sub.2 H.sub.5 C.sub.2       H.sub.4 --      ##STR62##       " 70 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.4 O NHC.sub.4 H.sub.9 "      71 " H H C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH OC.sub.2 H.sub.4 OH " 72       ##STR63##       H H C.sub.2 H.sub.4 OH C.sub.2 H.sub.4 -- NHC.sub.2 H.sub.4 NHCOC.sub.3      H.sub.7 violet 73 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 O NHC.sub.4      H.sub.9 " 74 " H H C.sub.2       H.sub.5      ##STR64##       O       ##STR65##       " 75       ##STR66##       H H C.sub.2 H.sub.4 Cl C.sub.2 H.sub.4 -- NHC.sub.3 H.sub.7 (n) " 76 "      H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 O NHC.sub.3 H.sub.7 (i) "  77 " H H      C.sub.2 H.sub.5 C.sub.2       H.sub.4 O      ##STR67##       " 78 " H H C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH NHC.sub.2 H.sub.4 Cl" 79       ##STR68##       H H C.sub.2 H.sub.4 OCOC.sub.3 H.sub.7 C.sub.2 H.sub.4 -- NHC.sub.4      H.sub.9 " 80 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 -- NHC.sub.2 H.sub.4      OH " 81 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 -- NHC.sub.3 H.sub.6      OCOCH.sub.3 " 82 " H H C.sub.2       H.sub.5 CH.sub.2 --      ##STR69##       " 83 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 -- NHC.sub.2 H.sub.4      OCOC.sub.3 H.sub.7 " 84 " H H C.sub.2       H.sub.5      ##STR70##       O NHCH.sub.3 " 85 " H HNCOCH.sub.3 C.sub.2 H.sub.4 OCONHCH.sub.3      C.sub.2 H.sub.4 O NHCH.sub.3 bluish violet 86 " H H C.sub.2 H.sub.4      COOC.sub.4 H.sub.9 C.sub.2 H.sub.4 O NHCH.sub.3 violet 87 " H H C.sub.2      H.sub.4 CN C.sub.2 H.sub.4 O NHCH.sub.3 reddish violet 88 " H Cl C.sub.2      H.sub.4 OCONHCH.sub.3 C.sub.2 H.sub.4 O NHCH.sub.3 " 89 " OC.sub.2      H.sub.5 NHCOCH.sub.3 C.sub.2 H.sub.4 OCONHCH.sub.3 C.sub.2 H.sub.4 O      NHCH.sub.3 bluish violet 90 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 O      N(CH.sub.3).sub.2 violet91 " H H       ##STR71##       C.sub.2       H.sub.4 O      ##STR72##       " 92 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 O OC.sub.4 H.sub.9 " 93 " H      NHCOCH.sub.3 C.sub.2 H.sub.4 OCOOC.sub.2 H.sub.5 C.sub.2 H.sub.4 O      OC.sub.2 H.sub.5 bluish violet 94 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4      O       ##STR73##       violet 95 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH NHCH.sub.3 "      96 " H CH.sub.3 C.sub.3 H.sub.6 NHCOCH.sub.3 C.sub.3       H.sub.6 NH NHCH.sub.3 " 97 " H H C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH      N(C.sub.4 H.sub.9).sub.2 " 98 " H H C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH      OCH.sub.3 " 99 " H H C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH OC.sub.2 H.sub.4      OH" 100 " H H C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH OC.sub.2 H.sub.4      OCONHCH.sub.3 " 101       ##STR74##       H H C.sub.3 H.sub.7 C.sub.2 H.sub.4 -- NHC.sub.2 H.sub.4 OCOCH.sub.3      bluish violet 102 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 O NH.sub.2 " 103      " H NHCOCH.sub.3 C.sub.2 H.sub.4 OCONHC.sub.4 H.sub.9 C.sub.2 H.sub.4 O      NHC.sub.4 H.sub.9 blue 104 " H C.sub.2 H.sub.5 CH.sub.3 C.sub.2 H.sub.4      O       ##STR75##       bluish violet 105 " H H C.sub.2       H.sub.5      ##STR76##       O OCH.sub.3 " 106 " H H C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH NHC.sub.4      H.sub.9 " 107 " H H C.sub.4 H.sub.9 C.sub.3       H.sub.6 NH      ##STR77##       " 108       ##STR78##       H H C.sub.2 H.sub.4 OCOC.sub.3 H.sub.7 C.sub.2       H.sub.4 -- N(CH.sub.3).sub.2 " 109 " H H       ##STR79##       C.sub.2 H.sub. 4 -- NHC.sub.2 H.sub.5 " 110 " H H C.sub.2 H.sub.5      C.sub.2 H.sub.4 -- NHC.sub.3 H.sub.6 OCOCH.sub.3 " 111 " H H C.sub.2      H.sub.5 C.sub.2 H.sub.4 -- NHC.sub.2 H.sub.4 OCOC.sub.3 H.sub.7 " 112 "      H H C.sub.2 H.sub.4 OCONHCH.sub.3 C.sub.2 H.sub.4 -- NHC.sub.2 H.sub.4      OCONHCH.sub.3 " 113 " H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 -- NHC.sub.2      H.sub.4 OCOOCH.sub.3 " 114 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.4      O NHCH.sub.3 " 115       ##STR80##       H H       ##STR81##       ##STR82##       O NHCH.sub.3 " 116 " CH.sub.3 H C.sub.2 H.sub.4 OCONHCH.sub.3 C.sub.2      H.sub.4 O NHCH.sub.3 " 117 " H H C.sub.2       H.sub.5      ##STR83##       O NHCH.sub.3 " 118 " H NHCHO C.sub.2 H.sub.4 OCONHC.sub.4 H.sub.9      C.sub.2 H.sub.4 O NHC.sub.4 H.sub.9 blue 119 " H H C.sub.2 H.sub.5      C.sub.2 H.sub.4 O NHC.sub.6 H.sub.13 bluish violet 120 " H H C.sub.2      H.sub.5       ##STR84##       O OCH.sub.3 " 121 "       ##STR85##       NHCOCH.sub.3 C.sub.2 H.sub.4 CN C.sub.2 H.sub.4 OOCH.sub.3 blue 122 " H      H CH.sub.2       CHOHCH.sub.3      ##STR86##       O OC.sub.2 H.sub.4 Cl bluish violet 123 " H CH.sub.3 C.sub.2 H.sub.5      C.sub.2 H.sub.4 O OC.sub.2 H.sub.4 OCH.sub.3 " 124 " H CH.sub.3 C.sub.2      H.sub.5 C.sub.3 H.sub.6 NH NHC.sub.4 H.sub.9 blue 125 " H H C.sub.2      H.sub.5 C.sub.3 H.sub.6 NC.sub.2 H.sub.4 CN NHCH.sub.3 " 126 " H      CH.sub.3 C.sub.3 H.sub.6 NHCONHCH.sub.3 C.sub.3 H.sub.6 NH NHCH.sub.3 "      127 " H H C.sub.2 H.sub.4 OCH.sub.3 C.sub.3       H.sub.6 NH      ##STR87##       " 128 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH OC.sub.2 H.sub.4      OH " 129 " H H C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH OC.sub.2 H.sub.4      OCOCH.sub.3 " 130 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH      OC.sub.4 H.sub.9 " 131 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH      OC.sub.2 H.sub.4 Cl " 132 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.6      NH OCH.sub.3 " 133       ##STR88##       H H C.sub.2 H.sub.4 OCONHCH.sub.3 C.sub.2 H.sub.4 -- NHC.sub.2 H.sub.5      " 134 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.4 -- NHC.sub.2 H.sub.4      OCOCH.sub.3 " 135 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.4 --      NHC.sub.2 H.sub.4 OCOC.sub.3 H.sub.7 " 136 " H CH.sub.3 C.sub.2 H.sub.5      C.sub.2 H.sub.4 -- NHC.sub.2 H.sub.4 NHCOC.sub.3 H.sub.7 " 137 " H      CH.sub.3 C.sub.2 H.sub.5 C.sub.2       H.sub.4 --      ##STR89##       " 138 " H CH.sub.3C.sub.2 H.sub.5 C.sub.2 H.sub.4 O NHCH.sub.3 " 139 "      H NHCOC.sub.3 H.sub.7 C.sub.2 H.sub.4 OCONHCH.sub.3 C.sub.2 H.sub.4 O      NHCH.sub.3 greenish blue 140 " H H C.sub.2       H.sub.5      ##STR90##       O NHCH.sub.3 blue 141 " C.sub.2 H.sub.5 H C.sub.2 H.sub.4 OH C.sub.2      H.sub.4 O NHCH.sub.3 " 142 " H CH.sub.3 C.sub.2       H.sub.5      ##STR91##       O NHCH.sub.3 " 143 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.4 O      NHC.sub.3 H.sub.7 (i) " 144 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.4      O NHC.sub.2 H.sub.4 CN " 145 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.2      H.sub.4 O N(C.sub.2 H.sub.4 Cl).sub.2 " 146 " H CH.sub.3 CH.sub.2      CHOHCH.sub.3       ##STR92##       O NHC.sub.4 H.sub.9 " 147 " H H C.sub.3 H.sub.7 C.sub.2 H.sub.4 O      NHC.sub.4       H.sub.9 " 148 " H CH.sub.3      ##STR93##       C.sub.2 H.sub.4 ONHC.sub.4 H.sub.9 " 149 " H H C.sub.2 H.sub.5 C.sub.2      H.sub.4 O       ##STR94##       " 150 " H CH.sub.3 C.sub.2 H.sub. 5 C.sub.2 H.sub.4 O OCH.sub.3 " 151 "      H H       ##STR95##       C.sub.2 H.sub.4 O OC.sub.3 H.sub.7 " 152 " H CH.sub.3 C.sub.2 H.sub.5      C.sub.2 H.sub.4 O OC.sub.3 H.sub.6 OCH.sub.3 " 153 " H CH.sub.3 C.sub.2      H.sub.5 C.sub.3 H.sub.6 NH NHCH.sub.3 greenish blue 154 " H CH.sub.3      C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH NHC.sub.4 H.sub.9 " 155 " H H C.sub.2      H.sub.5 C.sub.2 H.sub.4 NH NHC.sub.4 H.sub.9 blue 156 " H CH.sub.3      C.sub.2 H.sub.5 C.sub.3       H.sub.6 NH      ##STR96##       greenish blue 157 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH      NHC.sub.6 H.sub.13 " 158 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH      OCH.sub.3 " 159 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH OC.sub.2      H.sub.5 " 160 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.3       H.sub.6 NH      ##STR97##       " 161 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH OC.sub.2 H.sub.4      OH " 162 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.6 NH OC.sub.2      H.sub.4       OCH.sub.3 " 163      ##STR98##       H H C.sub.2 H.sub.5 C.sub.2 H.sub.4 O NHC.sub.2 H.sub.5 blue 164 " H H      C.sub.2 H.sub.4 CN C.sub.2 H.sub.4 O NHC.sub.4 H.sub.9 " 165 " H      CH.sub.3 C.sub.2 H.sub.5 C.sub.2       H.sub.4 --      ##STR99##       " 166 " H CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.4 -- NHC.sub.2 H.sub.4      OH " 

We claim:
 1. A dye having the formula ##STR100## in which: D¹ is 5-nitrobenzoisothiazolyl-(2,1), or5-cyano-7-nitrobenzoisothiazolyl-(1,2); B⁴ is hydrogen or methyl; R² is C₁ to C₄ alkyl, C₁ to C₄ alkoxyethyl, β-cyanoethyl or β-hydroxyethyl; A¹ is a direct bond, --NH-- or --O--; A² is NH--(C₁ to C₄)-alkyl, NH--C₂ H₄ OH, NH--C₃ H₆ OH, or ##STR101## or, when A¹ is --NH-- or --O--, is OCH₃, OC₂ H₅ or OC₂ H₄ OH; and Q is --C₂ H₄ --, --C₃ H₆ -- or --C₄ H₈ --.
 2. The dye having the formula: ##STR102##
 3. The dye having the formula: ##STR103##
 4. The dye having the formula: ##STR104##
 5. The dye having the formula: ##STR105##
 6. The dye having the formula: ##STR106##
 7. The dye having the formula: ##STR107##
 8. The dye having the formula: ##STR108## 